Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters.We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values,complicating efforts to quantify reduction.This study shows that Cr stable isotope fractionation caused by sorption is negligible.Equilibrium fractionation of Cr stable isotopes between dissolved Cr-(VI) and Cr(VI) adsorbed onto gamma-Al_2O_3 and goethite is less than 0.04 (~(53)Cr/~(52)Cr) under environmentally relevant pH conditions.Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations.A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume,leading to shifts in ~(53)Cr/~(52)Cr values.We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects.A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium.This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study.Cr isotope fractionation caused by speciation of Cr(VI) between HCrO_4~- and CrO_4~(2-) was also examined,and we conclude that it is not measurable.In the absence of isotope fractionation caused by equilibrium speciation and sorption,most of the variation in delta~(53)Cr values may be attributed to reduction,and reliable estimates of Cr reduction can be made.
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Department of Geology,University of Illinois at Urbana-Champaign,Urbana,Illinois,and Water Resources Division,U.S.Geological Survey,Menlo Park,California;
